Chromatographic Techniques in Polymer Characterization
Summary
Chromatographic techniques play a pivotal role in elucidating the structure and composition of synthetic and natural polymers. By exploiting differences in molecular size, crystallinity and chemical affinity, methods such as size-exclusion chromatography (SEC), high-performance liquid chromatography (HPLC) and thermal fractionation separate complex polymer mixtures into defined fractions. Thermal protocols, including temperature rising elution fractionation (TREF) and successive self-nucleation and annealing (SSA), discriminate species by crystallisation behaviour, while hyphenation of liquid chromatography with spectroscopic or pyrolitic detectors integrates structural and compositional analysis in a single workflow. Recent advances in cross-fractionation chromatography have unlocked access to species-specific crystallinity and comonomer distributions, and online coupling with techniques such as pyrolysis-gas chromatography has enabled molar mass–resolved chemical profiling. Together, these approaches underpin quality control in polymer production, inform the design of advanced materials and support the circular economy by precisely characterising recyclate streams.
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Recent work has introduced a lattice-cluster-theory-informed cross-fractionation chromatography method that combines high-throughput fractionation data with theoretical predictions to determine the degree of crystallinity of individual macromolecular species. Applied to linear low-density polyethylene and high-density polyethylene, this approach yields species-resolved crystallinity distributions that align closely with conventional measurements, offering new insight into branch-induced crystallisation phenomena.
Another study has demonstrated online hyphenation of size-exclusion chromatography with pyrolysis-gas chromatography (Py-GC). A multi-valve fractionation system transfers SEC eluate directly to a pyrolysis unit, enabling rapid, high-resolution analysis of monomer and comonomer distributions across a polymer’s molar mass spectrum. This technique reveals the molar mass–dependent incorporation of low-abundance comonomers in industrial copolymers with enhanced sensitivity and throughput.
A further development has refined the combination of temperature rising elution fractionation and gel permeation chromatography to improve quantitative determination of polyethylene and polypropylene in recycled blends. By correcting for polymer-specific detector responses and molecular weight-dependent elution overlaps, the method reduces compositional error from around 8 % to 2 %, while simultaneously mapping bivariate molecular weight and chemical composition distributions. This advancement enhances the reliability of recyclate quality assessment.
Chromatographic Techniques in Polymer Characterization publication trend
The graph below shows the total number of articles in chromatographic techniques in polymer characterization across all publications each year (not limited to Nature Index journals).
Technical terms
Chromatography: A set of separation techniques in which molecules are partitioned between a stationary phase and a mobile phase according to their physical or chemical properties.
Size-exclusion chromatography (SEC): A method that separates polymers by hydrodynamic volume, yielding molar mass distributions.
Cross-fractionation chromatography (CFC): An integrated protocol combining thermal fractionation and chromatographic separation to resolve individual macromolecular species.
Temperature rising elution fractionation (TREF): A thermal separation technique that fractionates semi-crystalline polymers by controlled heating to exploit differences in crystallisation temperatures.
Pyrolysis-gas chromatography (Py-GC): A combined approach in which polymer fragments generated by pyrolysis are analysed by gas chromatography to determine chemical composition.
References
- Lattice-Cluster-Theory-Informed Cross-Fractionation Chromatography Revealing Degree of Crystallinity of Single Macromolecular Species. ACS Macro Letters (2024).
- Online hyphenation of size-exclusion chromatography and pyrolysis-gas chromatography for polymer characterization. Journal of Chromatography A (2023).
- A novel approach for accurate determination of polyethylene and polypropylene content in polyolefin blends and recyclates by cross-fractionation chromatography. Polymer Testing (2024).
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